CN104418316A - Carbon nanotube sponge body and preparation method thereof - Google Patents
Carbon nanotube sponge body and preparation method thereof Download PDFInfo
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- CN104418316A CN104418316A CN201310377860.2A CN201310377860A CN104418316A CN 104418316 A CN104418316 A CN 104418316A CN 201310377860 A CN201310377860 A CN 201310377860A CN 104418316 A CN104418316 A CN 104418316A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28042—Shaped bodies; Monolithic structures
- B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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Abstract
A preparation method of a carbon nanotube sponge body comprises the steps: a carbon nanotube film structure and an oxidation solution are provided, the carbon nanotube film structure comprises a plurality of carbon nanotubes, self-supporting structures among the plurality of carbon nanotubes are formed through mutual attraction by Van der Waals force, and the oxidation solution is prepared from an oxidant and hydrogen peroxide; the carbon nanotube film structure is soaked into the oxidation solution for treating, and a preform is formed; and in a vacuum environment, the preform is subjected to freeze drying. The invention also provides the carbon nanotube sponge body prepared by the method.
Description
Technical field
The present invention relates to a kind of carbon nanotube cavernous body and preparation method thereof.
Background technology
Since 1991 Japanese Scientists Sumio Iijima Late Cambrian carbon nanotube (Carbon Nanotube, CNT), be that the nano material of representative causes people with the structures and characteristics of its uniqueness and pays close attention to greatly with carbon nanotube.In recent years, along with deepening continuously of carbon nanotube and nano materials research, its broad prospect of application constantly displayed.
But the carbon nanotube generally prepared is microtexture, it is being macroscopically Powdered or particulate state, is unfavorable for the macroscopic view application of carbon nanotube.Therefore, structure carbon nanotube being assembled into macro-scale is significant for the macroscopic view application of carbon nanotube.
In prior art, the carbon nanotube structure of macroscopic view mainly contains carbon nano-tube film.Described carbon nano-tube film obtains for directly pulling from a carbon nano pipe array.Described carbon nano-tube film is for consist of the end to end carbon nanotube of Van der Waals force multiple.Described carbon nano-tube film has the characteristics such as lightweight, porous, high strength and specific surface area are large, makes it have a good application prospect in fields such as absorption, filtrations.But the adsorption process of carbon nano-tube film is generally physical adsorption, and absorption property is more weak, therefore the absorption property of described carbon nano-tube film needs to be improved further.
Summary of the invention
In view of this, necessaryly a kind of carbon nanotube cavernous body and preparation method thereof had compared with high absorption property is provided.
A kind of preparation method of carbon nanotube cavernous body, comprise: a carbon nanotube membrane-like structure and an oxidizing solution are provided, this carbon nanotube membrane-like structure comprises multiple carbon nanotube, to be attracted each other formation one self supporting structure by Van der Waals force between the plurality of carbon nanotube, described oxidizing solution is configured by an oxygenant and hydrogen peroxide and forms, and described oxygenant is for being oxidized described multiple carbon nanotube and forming multiple functional group on its surface; Described carbon nanotube membrane-like structure is soaked in described oxidizing solution and processes, form a precast body; And under vacuum conditions, lyophilize is carried out to described precast body.
A kind of carbon nanotube cavernous body, comprise: multiple carbon nanotube and be formed at described carbon nano tube surface and equally distributed multiple carboxyl and multiple hydroxyl, to be attracted each other formation one self supporting structure by Van der Waals force between the plurality of carbon nanotube, multiple micropore is formed between adjacent carbon nanotube, wherein, the mass percentage of described carboxyl is 10-20%, and the mass percentage of described hydroxyl is 5-15%, and the diameter of described micropore is greater than 100 microns.
Compare with prior art, the described carbon nanotube cavernous body in the present invention has multiple hydrophilic functional group, therefore this carbon nanotube cavernous body has good absorption property, can be widely used in the fields such as siccative.In addition, because carbon nanotube structure has self-supporting performance, therefore this carbon nanotube cavernous body has stronger mechanical property, and is the membrane structure of a macroscopic view, therefore, various field can be applied to easily.Finally, the preparation method of the described carbon nanotube cavernous body in the present invention, by described carbon nanotube membrane-like structure being soaked in oxidisability solvent that oxygenant and hydrogen peroxide formed, thus can obtain carbon nanotube cavernous structure that is loose, porous; In addition, can prevent carbon nanotube cavernous body from caving in by vacuum lyophilization.
Accompanying drawing explanation
The method flow diagram of the described carbon nanotube cavernous body of preparation that Fig. 1 provides for the embodiment of the present invention.
The SEM photo of the carbon nanotube membrane adopted in the method for the described carbon nanotube cavernous body of preparation that Fig. 2 provides for the embodiment of the present invention.
The microphotograph of the carbon nanotube membrane adopted in the method for the described carbon nanotube cavernous body of preparation that Fig. 3 provides for the embodiment of the present invention.
The SEM photo of the carbon nanotube laminate adopted in the method for the described carbon nanotube cavernous body of preparation that Fig. 4 provides for the embodiment of the present invention.
The SEM photo of the carbon nanotube waddingization film adopted in the method for the described carbon nanotube cavernous body of preparation that Fig. 5 provides for the embodiment of the present invention.
The photo of the described carbon nanotube cavernous body that Fig. 6 provides for the embodiment of the present invention.
The microphotograph of the described carbon nanotube cavernous body that Fig. 7 provides for the embodiment of the present invention.
Main element nomenclature
Nothing
Following embodiment will further illustrate the present invention in conjunction with above-mentioned accompanying drawing.
Embodiment
Please refer to Fig. 1, the embodiment of the present invention provides a kind of preparation method of carbon nanotube cavernous body, comprise the following steps: (S10), one carbon nanotube membrane-like structure and an oxidizing solution are provided, this carbon nanotube membrane-like structure comprises multiple carbon nanotube, to be attracted each other formation one self supporting structure by Van der Waals force between the plurality of carbon nanotube, described oxidizing solution is configured by an oxygenant and hydrogen peroxide and forms; (S11), described carbon nanotube membrane-like structure is soaked in described oxidizing solution and processes, form a precast body; And (S12), under vacuum conditions, lyophilize is carried out to described precast body.
Step S10, provides a carbon nanotube membrane-like structure and an oxidizing solution.
Described carbon nanotube membrane-like structure is a self supporting structure.Described self-supporting is that described carbon nanotube membrane-like structure does not need large-area carrier supported, as long as and relatively both sides provide support power can be unsettled on the whole and keep self membranaceous state, by this carbon nanotube membrane-like structure be placed in (or being fixed on) keep at a certain distance away arrange two supporters on time, the carbon nanotube membrane-like structure between two supporters can the membranaceous state of unsettled maintenance self.Mainly through there is the carbon nanotube that attracted each other by Van der Waals force in carbon nanotube membrane-like structure and realizing in described self-supporting.Described carbon nanotube membrane-like structure is made up of multiple carbon nanotube, by Van der Waals force compact siro spinning technology between the plurality of carbon nanotube.Unordered or the ordered arrangement of the plurality of carbon nanotube.So-called lack of alignment refers to that the orientation of carbon nanotube is random.So-called ordered arrangement refers to that the orientation of carbon nanotube is regular.The thickness of described carbon nanotube membrane-like structure is not limit.Described carbon nanotube membrane-like structure has multiple micropore, and the diameter of described micropore is less than 10 microns.
Described carbon nanotube membrane-like structure can be the carbon nanotube membrane of multilayer laminated setting.Refer to Fig. 2-3, the self supporting structure that described single carbon nanotube membrane is made up of some carbon nanotubes.Described some carbon nanotubes are arranged of preferred orient substantially in the same direction, described in be arranged of preferred orient refer to most of carbon nanotube in carbon nanotube membrane overall bearing of trend substantially in the same direction.And the overall bearing of trend of described most of carbon nanotube is basically parallel to the surface of carbon nanotube membrane.Further, in described carbon nanotube membrane, most of carbon nanotube is joined end to end by Van der Waals force.Particularly, in the most of carbon nanotubes extended substantially in the same direction in described carbon nanotube membrane, each carbon nanotube and carbon nanotube adjacent are in the direction of extension joined end to end by Van der Waals force.Certainly, there is the carbon nanotube of minority random alignment in described carbon nanotube membrane, these carbon nanotubes can not form obviously impact to the overall orientation arrangement of carbon nanotube most of in carbon nanotube membrane.Described self-supporting is that carbon nanotube membrane does not need large-area carrier supported, as long as and relatively both sides provide support power can be unsettled on the whole and keep self membranaceous state, by this carbon nanotube membrane be placed in (or being fixed on) keep at a certain distance away arrange two supporters on time, the carbon nanotube membrane between two supporters can the membranaceous state of unsettled maintenance self.Described self-supporting mainly through exist in carbon nanotube membrane continuously through Van der Waals force join end to end extend arrangement carbon nanotube and realize.
Particularly, the most carbon nanotubes extended substantially in the same direction in described carbon nanotube membrane, and nisi linearity, can be suitable bend; Or and non-fully arranges according on bearing of trend, can be suitable depart from bearing of trend.Therefore, can not get rid of between carbon nanotube arranged side by side in the most carbon nanotubes extended substantially in the same direction of carbon nanotube membrane and may there is part contact.
Particularly, described carbon nanotube membrane comprise multiple continuously and the carbon nanotube fragment aligned.The plurality of carbon nanotube fragment is joined end to end by Van der Waals force.Each carbon nanotube fragment comprises multiple carbon nanotube be parallel to each other, and the plurality of carbon nanotube be parallel to each other is combined closely by Van der Waals force.This carbon nanotube fragment has arbitrary length, thickness, homogeneity and shape.Carbon nanotube in this carbon nanotube membrane is arranged of preferred orient in the same direction.In addition, because this carbon nanotube membrane has larger specific surface area, therefore, this carbon nanotube membrane has larger viscosity.
Be appreciated that, because described carbon nanotube membrane-like structure comprises the carbon nanotube membrane of multilayer laminated setting, and the carbon nanotube in every layer of carbon nanotube membrane is arranged of preferred orient along a direction, therefore, there is an intersecting angle α, 0 °≤α≤90 ° between the carbon nanotube in adjacent two layers carbon nanotube membrane.In this carbon nanotube membrane-like structure, the number of plies of carbon nanotube membrane is not limit, and is preferably more than 100 layers.In the present embodiment, described carbon nanotube membrane-like structure by 150 layer by layer the folded carbon nanotube membrane arranged form, and the extending substantially in the same direction of carbon nanotube in carbon nanotube membrane-like structure.
Be appreciated that described carbon nanotube membrane-like structure also can select carbon nanotube laminate or carbon nanotube waddingization film.
Described carbon nanotube laminate comprises equally distributed carbon nanotube, this carbon nanotube is unordered, in the same direction or different directions be arranged of preferred orient.Refer to Fig. 4, preferably, the carbon nanotube in described carbon nanotube laminate extends substantially in the same direction and is parallel to the surface of this carbon nanotube laminate.Carbon nanotube in described carbon nanotube laminate is mutually overlapping, thus makes the surface of described carbon nanotube laminate comparatively coarse.Attracted each other by Van der Waals force between carbon nanotube in described carbon nanotube laminate.This carbon nanotube laminate has good snappiness, can become arbitrary shape and do not break by bending fold.Described carbon nanotube laminate and preparation method thereof refers to disclosed in 3 days December in 2008, and publication number is the Chinese invention patent application prospectus of CN101314464A.
Refer to Fig. 5, described carbon nanotube waddingization film comprises the carbon nanotube be mutually wound around.Attracted each other by Van der Waals force between this carbon nanotube, be wound around, thus make the surface of described carbon nanotube waddingization film comparatively coarse.Carbon nanotube in described carbon nanotube waddingization film for being uniformly distributed, random arrangement.Described carbon nanotube waddingization film and preparation method thereof can see No. CN101284662Bth, China's Mainland patent announcement.
Described oxidizing solution is configured by an oxygenant and hydrogen peroxide and forms.Described oxygenant is for being oxidized the plurality of carbon nanotube and forming multiple functional group on its surface.Described oxygenant can for nitric acid, the vitriol oil, hypochlorous acid, chloric acid, chlorous acid, perchloric acid, nitrous acid, potassium permanganate, potassium bichromate or other there is the material of oxidisability.In the present embodiment, described oxygenant is concentration is 98%(mass percent) the vitriol oil, and the concentration of described hydrogen peroxide is 30%.The volume ratio of described hydrogen peroxide and the vitriol oil is between 1:2 to 1:5.Preferably, the volume ratio of described hydrogen peroxide and the vitriol oil is between 1:2 to 1:3.In the present embodiment, the volume ratio of described hydrogen peroxide and the vitriol oil is about 3:7.
Step S11, is soaked in described carbon nanotube membrane-like structure in described oxidizing solution and processes, form a precast body.
Describedly carbon nanotube membrane-like structure is soaked in the treatment time in described oxidizing solution and does not limit, can select according to the oxidisability of oxidizing solution; That is, when the oxygenant that selective oxidizing is stronger, as concentrated nitric acid etc., the shorter treatment time can be selected; When the oxygenant that selective oxidizing is more weak, as hypochlorous acid or chloric acid etc., the longer treatment time can be selected.In the present embodiment, the described treatment time is about 3 days.In addition, in order to reduce the treatment time, described oxidizing solution can also be heated to a preset temperature.Described preset temperature lower than 100 degrees Celsius, thus should can prevent oxidizing solution bumping.
Be appreciated that, because described oxidizing solution has certain oxidation susceptibility, therefore, in above-mentioned treating processes, this oxidizing solution can infiltrate the inside of described carbon nanotube membrane-like structure, thus make the surface of at least part of carbon nanotube in carbon nanotube membrane-like structure can be partially oxidized, thus form the functional group such as hydroxyl and carboxyl in described carbon nano tube surface.Preferably, the surface of all in described carbon nanotube membrane-like structure carbon nanotubes is all partially oxidized.In addition, in above-mentioned treating processes, hydrogen peroxide can be decomposed to form oxygen, and this oxygen can be assembled and be adsorbed in the surface of carbon nanotube in described carbon nanotube membrane-like structure, thus forms multiple bubble on the surface of described carbon nanotube.In the effect of this bubble, the gap in this carbon nanotube membrane-like structure between carbon nanotube can increase, thus makes this carbon nanotube membrane-like structure form a cellular vesicular structure.The enlarged-diameter more than 10 times of micropore in described precast body, that is, in described precast body, the diameter of micropore is more than or equal to 100 microns, and preferably, in described precast body, the diameter of micropore is more than or equal to 200 microns and is less than or equal to 500 microns.In addition, the volume of described precast body can enlarge markedly, and the volume of this precast body can increase more than 200%.
After forming described precast body, also comprise the step that described precast body is washed further.Particularly, described precast body is transferred to washing in a deionized water extremely neutral, thus remove the oxidizing solution in described precast body.
Step S12, under vacuum conditions, carries out lyophilize to described precast body.
Described cryodesiccated step is carried out to precast body, comprising: described precast body is put into a freeze drier, vacuumizes, and be chilled to less than-40 DEG C, and be incubated 1-5 hour; And described precast body is progressively increased the temperature to room temperature stage by stage, and when arriving every phase temperature dry 1-10 hour.
Particularly, described precast body is put into a freeze drier, and is chilled to-60 DEG C; Be evacuated to about 30pa, now, be warming up to-25 DEG C simultaneously, dry 2 hours; Be warmed up to-20 DEG C, dry 2 hours; Be warmed up to-15 DEG C, dry 2 hours; Be warmed up to-10 DEG C, dry 2 hours; Be warmed up to-5 DEG C, dry 2 hours; Be warmed up to 0 DEG C, dry 2 hours; Be warmed up to 5 DEG C, dry 2 hours; Be warmed up to 10 DEG C, dry 2 hours; Be warmed up to 15 DEG C, dry 2 hours; And, close vacuum system, open freeze drier intake valve, take out sample, obtain described carbon nanotube cavernous body.Be appreciated that and can prevent described precast body from caving in by vacuum lyophilization, be conducive to forming fluffy carbon nanotube cavernous body.
The preparation method of the described carbon nanotube cavernous body that the invention process provides has the following advantages: first, by described carbon nanotube membrane-like structure being soaked in oxidisability solvent that oxygenant and hydrogen peroxide formed, thus the carbon nanotube cavernous structure that loose, porous, light weight and surface have very strongly adherent can be obtained; Secondly, the functional group in described carbon nanotube cavernous body can be prevented by vacuum lyophilization destroyed and prevent carbon nanotube cavernous body from caving in; Finally, the raw material sources in the present embodiment is extensive, therefore the preparation method of this carbon nanotube cavernous body also has the features such as technique is simple, with low cost, is applicable to wide range of industrial applications.
Refer to Fig. 6-7, the embodiment of the present invention provides a kind of carbon nanotube cavernous body.Described carbon nanotube cavernous body is the vesicular structure of a self-supporting, and it comprises multiple carbon nanotube and is formed at described carbon nano tube surface and equally distributed multiple functional group.In described carbon nanotube cavernous body, the diameter of micropore is greater than 100 microns, and preferably, in described carbon nanotube cavernous body, the diameter of micropore is more than or equal to 200 microns and is less than or equal to 500 microns.To be attracted each other formation one self supporting structure by Van der Waals force between described multiple carbon nanotube.The mass percentage that described functional group accounts for carbon nanotube cavernous body can be 15-35%.Described functional group can be carboxyl and/or hydroxyl.Described multiple carboxyl and multiple hydroxyl are evenly distributed in the inside of described cavernous body and surface.The mass percentage that described carboxyl accounts for carbon nanotube cavernous body can be 10-20%, and the mass percentage that described hydroxyl accounts for carbon nanotube cavernous body can be 5-15%.In the present embodiment, the mass percentage that described carboxyl accounts for carbon nanotube cavernous body is about 12%, and the mass percentage that described hydroxyl accounts for carbon nanotube cavernous body is about 7%.The specific surface area of described carbon nanotube cavernous body can be greater than 200 square metres every gram, much larger than the specific surface area of carbon nanotube membrane-like structure, that is, and 170 square metres every gram.In the present embodiment, the specific surface area of described carbon nanotube cavernous body is about 220 square metres every gram.
Because described carbon nanotube cavernous body has multiple hydrophilic functional group, therefore this carbon nanotube cavernous body has good absorption property, can be widely used in the fields such as siccative.In addition, described carbon nanotube cavernous body can also be reused, thus can improve the utilization ratio of this carbon nanotube cavernous body.In addition, because carbon nanotube structure has self-supporting performance, therefore this carbon nanotube cavernous body has stronger snappiness, and is the membrane structure of a macroscopic view, therefore, various field can be applied to easily.
In addition, those skilled in the art also can do other changes in spirit of the present invention, and certainly, these changes done according to the present invention's spirit, all should be included within the present invention's scope required for protection.
Claims (13)
1. a preparation method for carbon nanotube cavernous body, comprising:
There is provided a carbon nanotube membrane-like structure, this carbon nanotube membrane-like structure comprises multiple carbon nanotube, to be attracted each other formation one self supporting structure between the plurality of carbon nanotube by Van der Waals force;
There is provided an oxidizing solution, described oxidizing solution is configured by an oxygenant and hydrogen peroxide and forms;
Described carbon nanotube membrane-like structure is soaked in described oxidizing solution and processes, form a precast body; And
Under vacuum conditions, lyophilize is carried out to described precast body.
2. the preparation method of carbon nanotube cavernous body as claimed in claim 1, it is characterized in that, described oxygenant is selected from nitric acid, the vitriol oil, hypochlorous acid, chloric acid, chlorous acid, perchloric acid, nitrous acid, potassium permanganate and potassium bichromate.
3. the preparation method of carbon nanotube cavernous body as claimed in claim 2, is characterized in that, described oxidizing solution by concentration be 98% the vitriol oil and concentration be 30% hydrogen peroxide configure and form, and the volume ratio of hydrogen peroxide and the vitriol oil is between 1:2 to 1:5.
4. the preparation method of carbon nanotube cavernous body as claimed in claim 3, is characterized in that, described carbon nanotube membrane-like structure is soaked in described oxidizing solution and processes more than 3 days.
5. the preparation method of carbon nanotube cavernous body as claimed in claim 1, is characterized in that, described cryodesiccated step is carried out to precast body before, comprise further and use precast body described in deionized water wash.
6. the preparation method of carbon nanotube cavernous body as claimed in claim 1, is characterized in that, describedly carries out cryodesiccated step to precast body and comprises:
Described precast body is put into freeze drier and is chilled to less than-40 DEG C, and be incubated 1-5 hour; And
Described precast body is progressively increased the temperature to room temperature stage by stage, and when arriving every phase temperature dry 1-10 hour.
7. the preparation method of carbon nanotube cavernous body as claimed in claim 1, it is characterized in that, described carbon nanotube membrane-like structure comprises the carbon nano-tube film of multiple stacked setting, and by Van der Waals force compact siro spinning technology between multiple carbon nano-tube film.
8. a carbon nanotube cavernous body, comprise: multiple carbon nanotube and be formed at described carbon nano tube surface and equally distributed multiple carboxyl and multiple hydroxyl, to be attracted each other formation one self supporting structure by Van der Waals force between the plurality of carbon nanotube, multiple micropore is formed between adjacent carbon nanotube, it is characterized in that, the mass percentage of described carboxyl is 10-20%, and the mass percentage of described hydroxyl is 5-15%, and the diameter of described micropore is greater than 100 microns.
9. carbon nanotube cavernous body as claimed in claim 8, it is characterized in that, the mass percentage of described carboxyl is 12%, and the mass percentage of described hydroxyl is 7%.
10. carbon nanotube cavernous body as claimed in claim 8, it is characterized in that, the specific surface area of described carbon nanotube cavernous body is greater than 200 square metres every gram.
11. carbon nanotube cavernous bodies as claimed in claim 8, it is characterized in that, the diameter of described micropore is greater than 200 microns and is less than 500 microns.
12. carbon nanotube cavernous bodies as claimed in claim 8, is characterized in that, described multiple carboxyl and multiple hydroxyl are evenly distributed in the inside of described cavernous body and surface.
13. carbon nanotube cavernous bodies as claimed in claim 8, it is characterized in that, described cavernous body is cellular structures, and multiple micropore through hole is interconnected.
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| CN201310377860.2A CN104418316B (en) | 2013-08-27 | 2013-08-27 | Carbon nanotube sponge body and preparation method thereof |
| TW102131906A TWI593624B (en) | 2013-08-27 | 2013-09-05 | Carbon nanotube sponge and method for making the same |
| US14/096,533 US9102537B2 (en) | 2013-08-27 | 2013-12-04 | Carbon nanotube sponge and method for making the same |
| JP2014165368A JP5850445B2 (en) | 2013-08-27 | 2014-08-15 | Carbon nanotube sponge-like structure and method for producing the same |
| US14/713,313 US9669383B2 (en) | 2013-08-27 | 2015-05-15 | Carbon nanotube sponge |
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| CN201310377860.2A CN104418316B (en) | 2013-08-27 | 2013-08-27 | Carbon nanotube sponge body and preparation method thereof |
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| CN104418316B CN104418316B (en) | 2017-01-25 |
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Also Published As
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| TW201509793A (en) | 2015-03-16 |
| US20150065342A1 (en) | 2015-03-05 |
| US9669383B2 (en) | 2017-06-06 |
| JP5850445B2 (en) | 2016-02-03 |
| US9102537B2 (en) | 2015-08-11 |
| TWI593624B (en) | 2017-08-01 |
| JP2015044731A (en) | 2015-03-12 |
| CN104418316B (en) | 2017-01-25 |
| US20150258526A1 (en) | 2015-09-17 |
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